[go: up one dir, main page]

EP1245645B1 - Modification cristalline d'un colorant périnonique - Google Patents

Modification cristalline d'un colorant périnonique Download PDF

Info

Publication number
EP1245645B1
EP1245645B1 EP02005372A EP02005372A EP1245645B1 EP 1245645 B1 EP1245645 B1 EP 1245645B1 EP 02005372 A EP02005372 A EP 02005372A EP 02005372 A EP02005372 A EP 02005372A EP 1245645 B1 EP1245645 B1 EP 1245645B1
Authority
EP
European Patent Office
Prior art keywords
dye
formula
modification
parts
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP02005372A
Other languages
German (de)
English (en)
Other versions
EP1245645A3 (fr
EP1245645A2 (fr
Inventor
Stephan Dr. Michaelis
Josef-Walter Dr. Stawitz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanxess Deutschland GmbH
Original Assignee
Lanxess Deutschland GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lanxess Deutschland GmbH filed Critical Lanxess Deutschland GmbH
Publication of EP1245645A2 publication Critical patent/EP1245645A2/fr
Publication of EP1245645A3 publication Critical patent/EP1245645A3/fr
Application granted granted Critical
Publication of EP1245645B1 publication Critical patent/EP1245645B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/12—Perinones, i.e. naphthoylene-aryl-imidazoles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0025—Crystal modifications; Special X-ray patterns

Definitions

  • the invention relates to a novel crystal modification of a perinone dye of the formula (I), a process for its preparation and its use for the mass coloration of plastics.
  • JP-A-52005841 discloses the conversion of a pigment of the formula from the alpha to the beta form by heating the alpha form with stirring in the presence of an aromatic carboxylic acid in the heat.
  • US-A-2805957 discloses the preparation of substituted copper phthalocyanine compounds.
  • the dye of the formula (I) in the known ⁇ -modification is an often used and coloristically valuable dye for the mass coloration of plastics and other applications.
  • the known dye as powder has a low bulk density and shows an undesirable dust load during handling.
  • the production of a granule or powder by spray-drying is a aqueous slurries because of a low solids content in the slurry not economical.
  • the object of the present invention was therefore to remedy the known disadvantages of the dye of the formula (I).
  • Fig. 1 The X-ray diffraction pattern of the ⁇ -modification recorded with Cu-K ⁇ radiation is shown in Fig. 1 and that of the ⁇ -modification in Fig. 2.
  • a computer-controlled STOE STADI- ⁇ powderdiffractometer was used for recording.
  • the ⁇ -modification according to the invention can be prepared, for example, by reacting phthalic anhydride and 1,8-diaminonaphthalene in an organic solvent in the presence of trimellitic acid or derivatives thereof at a temperature of 90 to 200 ° C.
  • trimellitic acid or derivative is preferably 0.005 to 0.1, in particular 0.02 to 0.05 mole equivalents, based on 1 mole of 1,8-diaminonaphthalene.
  • Suitable organic solvents are preferably: N-methylpyrrolidone, phenol, dichlorobenzene, nitrobenzene, chlorobenzene and / or glycol, in particular N-methylpyrrolidone.
  • the reaction is preferably carried out at a temperature of 100 to 160 ° C.
  • trimellitic acid such as mineral acids or hydrochloric acid, sulfuric acid or phosphoric acid, but preferably organic acids other than trimellitic acid are used, for example aliphatic or aromatic carboxylic acids or sulfonic acids such as taurine or toluenesulfonic acid.
  • reaction accelerators are preferably used in an amount of 0.001 to 1, in particular 0.01 to 0.2 mol equivalents, based on 1,8-diaminonaphthalene.
  • the invention also relates to the product obtainable by the process according to the invention, whose X-ray diffraction pattern has lines at the same diffraction angles as given for the ⁇ -modification.
  • the procedure is to meter in 1,8-diaminonaphthalene at reaction temperature to a solution or suspension of phthalic anhydride and trimellitic acid or derivative in an organic solvent.
  • the 1,8-diaminonaphthalene can be added in dissolved form, for example in an organic solvent such as N-methyl-pyrrolidone, in molten or solid form.
  • the invention further relates to a process for the preparation of the dye of the formula (I) in the ⁇ -modification, which comprises reacting the dye of the formula (I) in the ⁇ -modification as described above in an organic solvent
  • a process for the preparation of the dye of the formula (I) in the ⁇ -modification which comprises reacting the dye of the formula (I) in the ⁇ -modification as described above in an organic solvent
  • an organic solvent for example, in one of the abovementioned solvents, in particular in N-methylpyrrolidone, preferably at a temperature of 80 to 160 ° C dissolves and precipitates the dye of formula (I) in the presence of trimellitic acid or derivatives thereof, preferably in the presence of a compound of formula II ,
  • the invention further relates to an aqueous dispersion containing 20 to 50 wt .-% of the dye of the formula I in the ⁇ -modification and 0.1 to 5 wt .-% of a dispersant, based on the dye contained in the dispersion.
  • Suitable dispersants are, in particular, the polyglycols disclosed in EP-A 488 933.
  • the polyglycol has a molecular weight of 900-15,000, in particular 5,000-8,000 g / mol, calculated from the OH number.
  • the polyglycol is a copolymer of propylene oxide and ethylene oxide.
  • the polyglycol is a copolymer of propylene oxide and ethylene oxide having an average molar mass, calculated from the OH number, of 2,000 to 10,000 g / mol.
  • the amount of polyglycol, based on the dry dye 1-3 wt .-%.
  • the advantage of the aqueous dispersion according to the invention lies in the setting of a higher dye content compared to a corresponding dispersion containing the dye of the formula I in the ⁇ -modification.
  • the aqueous dispersion may then be spray-dried, preferably using the spray-drying conditions mentioned in EP-A-488 933.
  • the invention therefore also relates to a solid preparation containing 95 to 99.9 wt .-% of dye of the formula I in the ⁇ -modification and 0.1 to 5 wt .-% of a dispersant, based on the dye.
  • the solid preparations according to the invention are preferably obtained by spray-drying the aqueous dispersion according to the invention.
  • the solid preparation according to the invention preferably contains 95 to 99.9% by weight of dye of the formula I in the ⁇ -modification and 0.1 to 5% by weight of a dispersant, the sum of dye of the formula I in the ⁇ -modification and dispersing agent, based on the solid preparation,> 96 wt .-%, preferably> 97, in particular> 99 wt .-% is.
  • the solid preparation is present as a powder or granules.
  • the dye of the formula (I) according to the invention in the ⁇ -modification is outstandingly suitable for dyeing plastics in the mass.
  • the dye of the formula (Ia) gives orange dyeings.
  • mass dyeing is understood in particular to mean processes in which the dyestuff is incorporated into the molten plastic mass, for example with the aid of an extruder, or in which the dye is already added starting components for the production of the plastic, for example monomers before the polymerization.
  • thermoplastics for example vinyl polymers, polyesters, polyamides and polyolefins, in particular polyethylene and polypropylene, or polycarbonates.
  • Suitable vinyl polymers are polystyrene, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, styrene-butadiene-acrylonitrile terpolymers, polymethacrylate, polyvinyl chloride, and the like.
  • polyesters such as polyethylene terephthalates, polycarbonates and cellulose esters.
  • polystyrene Preference is given to polystyrene, styrene copolymers, polycarbonates, polymethacrylates and polyamides. Particularly preferred is polystyrene, polyethylene and polypropylene.
  • the high molecular weight compounds mentioned may be present individually or in mixtures, as plastic compositions or melts.
  • the dyes of the invention are preferably used in finely divided form, but dispersants can be used but need not.
  • the dye (I) is used in the ⁇ -modification after the polymerization, it is preferably dry-mixed or ground with the plastic granules and this mixture is plasticized and homogenized, for example, on mixing rolls or in screws. But you can also add the dyes to the molten mass and distribute them homogeneously by stirring. The material thus pre-dyed becomes then processed as usual, for example by spinning to bristles, threads, etc. or by extrusion or by injection molding to form parts.
  • the dye of the formula (I) is resistant to polymerization catalysts, in particular peroxides, it is also possible to add the dye to the monomeric starting materials for the plastics and then to polymerize in the presence of polymerization catalysts.
  • the dye is preferably dissolved in the monomeric components or intimately mixed with them.
  • the dye of the formula (I) in the ⁇ -modification is preferably used for dyeing the said polymers in amounts of 0.0001 to 1 wt .-%, in particular 0.01 to 0.5 wt .-%, based on the amount of polymer, used.
  • pigments insoluble in the polymers e.g. Titanium dioxide
  • corresponding valuable muted colors can be obtained.
  • Titanium dioxide may be used in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the amount of polymer.
  • the process according to the invention gives transparent or opaque brilliant orange dyeings having good heat resistance and good light, weather and sublimation fastness.
  • the dyestuff of the formula (I) was prepared analogously to the procedure of Example 1 from EP-A 780 444.
  • the dye thus obtained is present in the ⁇ -modification and has the X-ray diffraction diagram according to FIG.
  • NMP N-methylpyrrolidone
  • 6 parts of toluenesulfonic acid and 100 parts of phthalic anhydride is added over a period of 4 Hours at 145 ° C, a solution of 110 parts of N-methyl-pyrrolidone and 89 parts of 1,8-diaminonaphthalene added dropwise.
  • a comparison of the properties of the dye of the formula (I) in the ⁇ -modification of Comparative Example 1 or 2 and the ⁇ -modification according to any of Examples 1 or 3 shows the following image.
  • ⁇ -modification ⁇ -modification Bulk density in g / cm 3 0.16 0.29 Filtration in the isolation of the dye from the reaction mixture Good very good (even without vacuum)
  • the ⁇ -modification can only be produced in a smaller amount than the ⁇ -modification, since in the ⁇ -modification stirring problems occur very quickly. This is not the case with the ⁇ -modification.
  • the ⁇ -modification also allows for a higher space-time yield.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paper (AREA)
  • Liquid Crystal (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Claims (8)

  1. Colorant de formule (I) sous la modification β
    Figure imgb0007
     qui présente, dans le diagramme de diffraction des rayons X (rayonnement Cu-Kα), des raies à des angles de diffraction 2θ (º) suivants :
    9,935 ; 12,734 ; 13,378 ; 24,033 ; 24,852 ; 27,455.
  2. Procédé de préparation du colorant selon la revendication 1, caractérisé en ce que de l'anhydride phtalique et du 1,8-diaminonaphtalène sont mis à réagir dans un solvant organique en présence d'acide trimellitique ou de ses dérivés à une température de 90 à 200ºC.
  3. Procédé selon la revendication 2, caractérisé en ce que l'on utilise de la N-méthylpyrrolidone en tant que solvant organique.
  4. Procédé selon la revendication 2, caractérisé en ce que la réaction est en outre réalisée en présence d'acide toluènesulfonique.
  5. Procédé de préparation du colorant selon la revendication 1, caractérisé en ce que le colorant de formule (I) sous la modification α, qui présente, dans le diagramme de diffraction des rayons X (rayonnement Cu-Kα), des raies à des angles de diffraction 2θ (º) suivants :
    9, 911 ; 11,799 ; 12,412 ; 13,150 ; 23,682 ; 24,122 ; 24,852 ; 26,765 ; 27,476,
    est dissous dans un solvant organique et le colorant de formule (I) précipite en présence d'acide trimellitique ou de ses dérivés.
  6. Dispersion aqueuse contenant de 30 à 50 % en poids du colorant selon la revendication 1 et de 0,1 à 5 % en poids d'un agent dispersant, par rapport au colorant sec selon la revendication 1.
  7. Préparations solides contenant de 95 à 99,9 % en poids du colorant selon la revendication 1 et de 0,1 à 5,0 % en poids d'un agent dispersant, dans chaque cas par rapport à la préparation.
  8. Utilisation du colorant selon la revendication 1 ou de la préparation selon la revendication 7 pour la coloration en masse de matières synthétiques.
EP02005372A 2001-03-29 2002-03-15 Modification cristalline d'un colorant périnonique Expired - Lifetime EP1245645B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10115404A DE10115404A1 (de) 2001-03-29 2001-03-29 Neue Kristallmodifikation eines Perinonfarbstoffes
DE10115404 2001-03-29

Publications (3)

Publication Number Publication Date
EP1245645A2 EP1245645A2 (fr) 2002-10-02
EP1245645A3 EP1245645A3 (fr) 2003-12-03
EP1245645B1 true EP1245645B1 (fr) 2006-05-03

Family

ID=7679463

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02005372A Expired - Lifetime EP1245645B1 (fr) 2001-03-29 2002-03-15 Modification cristalline d'un colorant périnonique

Country Status (7)

Country Link
US (1) US6846335B2 (fr)
EP (1) EP1245645B1 (fr)
JP (1) JP4187452B2 (fr)
CN (1) CN1379064A (fr)
CZ (1) CZ302782B6 (fr)
DE (2) DE10115404A1 (fr)
TW (1) TW593570B (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007302782A (ja) * 2006-05-11 2007-11-22 Ueno Fine Chem Ind Ltd フタロペリノン化合物
CN101565556B (zh) * 2009-03-23 2012-10-17 南通龙翔化工有限公司 一种溶剂橙60的制备方法
CN103275515B (zh) * 2013-06-18 2014-10-29 海宁市现代化工有限公司 一种橙色萘环酮染料及其制备方法
US10280366B2 (en) 2015-06-23 2019-05-07 Instituto Potosino DE Investigación Cientiffica y Technológica A.C. White light emitting material and method of preparation and uses thereof
JP6841298B2 (ja) * 2019-06-10 2021-03-10 セイコーエプソン株式会社 昇華転写用インクジェットインク組成物、並びに、染色物及びその製造方法
CN112592603A (zh) * 2020-12-22 2021-04-02 安徽清科瑞洁新材料有限公司 一种低污染制备溶剂橙60的绿色方法
US20250304795A1 (en) 2024-03-27 2025-10-02 Lanxess Deutschland Gmbh Sulfonyl-bridged perinones

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2805957A (en) * 1953-11-12 1957-09-10 Du Pont Phthalocyanine pigments
US2955902A (en) * 1955-07-20 1960-10-11 Sandoz Ag Process for the dyeing of polyester fibers
US2994697A (en) * 1957-04-20 1961-08-01 Hoechst Ag New dyestuffs of the 1, 8-naphthalene dicarboxylic acid series
FR1430705A (fr) * 1964-04-16 1966-03-04 Basf Ag Colorants de la série de la phtalopérinone
DE1282214B (de) * 1964-04-16 1968-11-07 Basf Ag Verfahren zur Herstellung von Farbstoffen der Phthaloperinonreihe
CH480417A (de) * 1965-08-23 1969-10-31 Ciba Geigy Verfahren zur Herstellung basischer Perinonfarbstoffe
JPS581151B2 (ja) * 1975-07-03 1983-01-10 大日精化工業株式会社 ガンリヨウノケツシヨウセイシツヘンカンホウホウ
DE4038002A1 (de) 1990-11-29 1992-06-04 Bayer Ag Verfahren zur herstellung von verbesserten farbstoffgranulaten
DE19548453A1 (de) * 1995-12-22 1997-06-26 Bayer Ag Verfahren zur Herstellung polycyclischer Verbindungen

Also Published As

Publication number Publication date
US6846335B2 (en) 2005-01-25
CZ302782B6 (cs) 2011-11-02
US20020193577A1 (en) 2002-12-19
CZ20021128A3 (cs) 2002-11-13
EP1245645A3 (fr) 2003-12-03
JP4187452B2 (ja) 2008-11-26
DE10115404A1 (de) 2002-10-02
TW593570B (en) 2004-06-21
JP2002348495A (ja) 2002-12-04
EP1245645A2 (fr) 2002-10-02
CN1379064A (zh) 2002-11-13
DE50206616D1 (de) 2006-06-08

Similar Documents

Publication Publication Date Title
EP0256983B1 (fr) Solutions solides de pyrrolo-[3,4-c]-pyrroles
DE69213368T2 (de) Verfahren zur Konditionierung organischer Pigmente
EP0296111B1 (fr) Pigments organiques revêtus d'oxydes métalliques
DE60121993T2 (de) Rheologieverbesserer und rheologisch verbesserte pigmentpräparate
EP0225553B1 (fr) Laque de colorant azoique
US4692189A (en) Novel compositions based on indanthrone blue pigments
EP1664203B1 (fr) Compositions pigmentaires contenant des pigments organiques et des pigments inorganiques
DE69701232T2 (de) Ternäre feste Lösungen von 1,4-Diketopyrrolopyrrolen und Chinacridonen
DE69416219T2 (de) Herstellung von pigmentärem 2,9-Dichlorchinacridon
EP0408499A2 (fr) Procédé pour conditionner des pigments organiques
EP0277914B1 (fr) Solutions solides de pyrrolo-[3,4-c]-pyrroles avec des quinacridones
EP0296107A2 (fr) Pigments organiques revêtus d'éthyle cellulose réticulée
EP1245645B1 (fr) Modification cristalline d'un colorant périnonique
EP0827986B1 (fr) Périnone, quinophtalone et périnone-quinophtalone pontées
DE69222262T2 (de) Neue feste Lösungen von Kupferphthalocyaninverbindungen
DE2256485C3 (de) Kupferphthalocyaninpigmente sowie ihre Verwendung
DE69217295T2 (de) Modifiziertes Gamma-Chinacridonpigment
EP0673979B1 (fr) Colorants fluorescents ayant des groupes cyanimino
DE2826268A1 (de) Verfahren zum faerben von thermoplastischen harzen
EP0376158B1 (fr) Solution solide cristalline de pigments du type anthanthrone, leurs procédés de préparation et leur application
EP0337435B1 (fr) Procédé de fabrication de pigments de dicétopyrrolopyrrole couvrants
EP0656403B1 (fr) Composition pigmentaire à base de dicetopyrrolopyrrolo et de résine aminoalkyleacrylique
EP0042819B1 (fr) Procédé de préparation de bis(3,5-diméthylphénylimide) de l'acide pérylène tétracarboxylique opaque
EP1293538B1 (fr) Procédé de préparation de colorants styryliques
DE2257672C3 (de) Verwendung eines Anthrachinonoxadiazols als Pigmentfarbstoff

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

RIC1 Information provided on ipc code assigned before grant

Ipc: 7C 09B 57/12 B

Ipc: 7C 09B 67/22 B

Ipc: 7C 09B 67/48 A

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BAYER CHEMICALS AG

17P Request for examination filed

Effective date: 20040603

AKX Designation fees paid

Designated state(s): CH DE ES FR GB LI

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: LANXESS DEUTSCHLAND GMBH

17Q First examination report despatched

Effective date: 20050701

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): CH DE ES FR GB LI

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060503

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: E. BLUM & CO. PATENTANWAELTE

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 50206616

Country of ref document: DE

Date of ref document: 20060608

Kind code of ref document: P

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060814

GBV Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed]

Effective date: 20060503

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20070206

REG Reference to a national code

Ref country code: CH

Ref legal event code: PFA

Owner name: LANXESS DEUTSCHLAND GMBH

Free format text: LANXESS DEUTSCHLAND GMBH# #51369 LEVERKUSEN (DE) -TRANSFER TO- LANXESS DEUTSCHLAND GMBH# #51369 LEVERKUSEN (DE)

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 50206616

Country of ref document: DE

Owner name: LANXESS DEUTSCHLAND GMBH, DE

Free format text: FORMER OWNER: LANXESS DEUTSCHLAND GMBH, 51373 LEVERKUSEN, DE

Effective date: 20131113

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20140312

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20140311

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20140417

Year of fee payment: 13

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 50206616

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20151130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150331

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20151001

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150331